US4818413A - Biocide water treatment having reduced copper corrosion - Google Patents

Biocide water treatment having reduced copper corrosion Download PDF

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Publication number
US4818413A
US4818413A US07/081,857 US8185787A US4818413A US 4818413 A US4818413 A US 4818413A US 8185787 A US8185787 A US 8185787A US 4818413 A US4818413 A US 4818413A
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Prior art keywords
copper
rate
bromide
discharge
chlorine
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Expired - Lifetime
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US07/081,857
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English (en)
Inventor
Richard L. Hoover
Mark A. Bush
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ChampionX LLC
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Nalco Chemical Co
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Priority to US07/081,857 priority Critical patent/US4818413A/en
Assigned to NALCO CHEMICAL COMPANY reassignment NALCO CHEMICAL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BUSH, MARK A., HOOVER, RICHARD L.
Priority to AU20042/88A priority patent/AU598176B2/en
Priority to NZ225663A priority patent/NZ225663A/xx
Priority to EP88112729A priority patent/EP0302501A1/fr
Priority to BR8803873A priority patent/BR8803873A/pt
Priority to JP63193561A priority patent/JPH01119391A/ja
Priority to EP88121040A priority patent/EP0373249A1/fr
Publication of US4818413A publication Critical patent/US4818413A/en
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation

Definitions

  • the present invention generally relates to the treatment of industrial process water to control the growth and deposit of microorganisms, and more particularly to the treatment of industrial process water with a chlorine containing oxidant and a bromide salt in such a way that copper corrosion is reduced to a certain minimal level.
  • Industrial process waters are contaminated with microorganisms, particularly bacteria.
  • Industrial process waters are used in the cooling towers and condensers of electrical power plants, and in many manufacturing plants such as paper mills.
  • Fouling caused by microorganisms in the cooling systems of power plants is an especially troublesome problem.
  • the temperatures inside a typical condenser provide an ideal environment for the growth of microorganisms.
  • Even a few thousandths of an inch of slime deposit on a condenser tube has been shown to affect condenser efficiency, plant heat rate and maintenance costs.
  • the slime layer forms a sticky substance which allows silt and other particles to adhere to the surface of the condenser tube.
  • the heat transfer loss due to this insulating layer has been estimated to cost the electric utility industry up to $400 million a year in additional fuel costs.
  • corrosion and pitting can occur under the slime and silt deposits, causing long term damage to the cooling system.
  • TRC total residual chlorine
  • biocide alternatives to chlorination which are capable of reducing the TRC value to 0.2 mg/l. These alternatives include water treatment with sodium sulfite, sulfur dioxide, chlorine dioxide, and bromine. But in the amounts required for comparable biocide activity, sodium sulfite, sulfur dioxide, and chlorine dioxide are far more expensive than chlorine. Bromine is also more expensive than chlorine, but its biocide activity is greater. Consequently, bromine is one of the most cost-effective biocide alternatives to chlorination.
  • bromine is not due to the elemental bromine itself, since it is well known that chlorine is a much stronger oxidant than bromine.
  • the biocide activity is primarily due to their respective reaction products with water, which are hypochlorous acid and hypobromous acid.
  • Bromine and chlorine are also compatible biocides, and can be used simultaneously in various amounts.
  • Elemental bromine which is a liquid, can be injected directly into the process water stream to provide biocide treatment.
  • chlorine both the chlorine and the bromine in the form of fuming bromine chloride liquid can be injected simultaneously into the process water stream.
  • fuming bromine chloride is relatively dangerous to handle.
  • a safe and economical method of providing hypobromous and hypochlorous acid in process water is to chlorinate the process water in the usual fashion, and to simultaneously inject a bromide salt.
  • the hypochlorous acid produced during chlorination reacts with the bromide ions in solution to form hypobromous acid and chloride ions.
  • the reactants should be relatively concentrated, and therefore the hypobromous acid (or hypobromite) is produced as a treating solution which is injected into the process water stream. Due to the fact that hypochlorous acid is consumed in the reaction, the chlorine residual to bromide ratio can be varied to obtain a system which contains anywhere from a total bromine residual to a total chlorine residual. This is particularly important in systems with high ammonia levels since bromamines degrade more rapidly, and consequently, are not as persistent in the environment.
  • a solution is prepared including a chlorine containing oxidant chosen from the group consisting of an inorganic hypochlorite salt, hypochlorous acid, and chlorine.
  • a solution is prepared containing a water-soluble inorganic bromide such as sodium bromide, and an anionic polymeric dispersant such as low molecular weight copolymers of acrylic acid or methyl or ethyl acetate.
  • a metering and pumping system for low viscosity fluids is provided to inject the sodium bromide and dispersant solution into the chlorination system.
  • the preferred point of injection is either before or after the chlorination injection so that the sodium bromide and the chlorine containing oxidant are mixed together in a relatively high concentration aqueous solution.
  • a brand of sodium bromide and dispersant mixture is sold commercially under the trademark "Acti-Brom" by Nalco Chemical Company, One Nalco Center, Naperville, Ill., 60566-1024. As a starting dosage, it is recommended that the chlorine dosage be reduced by 50 to 75%.
  • the treatment time to prevent biofouling in power plant cooling systems is about two hours per day.
  • the chemical feed rates for example, are 2400 pounds per day of chlorine, and 170 pounds per day of sodium bromide.
  • Nalco Chemical Company has developed and used a mobile laboratory including monitoring equipment for measuring critical water cooling variables (such as pH, conductivity, fouling factors, and corrosion rates) and a computer programmed for data acquisition and correlation of changes in water chemistry or other variables to fouling and corrosion problems.
  • the computer program includes a model of the operation of a cooling water system which considers the concentrating effect of the cooling tower and possible ranges of pH and temperature. The model predicts the solubility of up to 150 different minerals including calcium, chloride, copper fluoride, iron, magnesium, sodium, ammonia, nitrate, phosphate, sulfide, silicate, sulfate, and zinc.
  • Corrosion rates are important for monitoring the depreciation of the condensers. So that corrosion will not substantially reduce the expected lifetime of the cooling system, it is desirable to limit the corrosion rate to less than 0.1 mill per year.
  • the primary object of the invention is to provide an economical biocide water treatment program for reducing copper corrosion to a certain discharge limit.
  • the copper corrosion rate is minimized to a certain discharge limit by providing a chlorine-bromide treatment in which the chemical feed rate of bromide is increased to an amount required to decrease the copper corrosion rate to the rate required to meet the discharge limit.
  • the inventors made the unexpected and surprising discovery that an increase in the chemical feed rate of bromide--even when the chlorine feed rate is constant--has the effect of reducing copper corrosion. Therefore, this effect is useful for adjusting the copper corrosion rate to an optimum rate to most economically achieve a certain discharge limit.
  • the biocide water treatment program includes the steps of measuring the copper corrosion rate during a chlorine-bromide treatment interval, computing the value of copper discharge from the measured copper corrosion rate, comparing the computed value of copper discharge to the discharge limit, and adjusting the bromide chemical feed rate based on the comparison, to thereby economically achieve an amount of copper discharge within the discharge limit.
  • FIG. 1 is a graph of the relative copper corrosion rate, the cost, and the biocide activity of a chlorine-bromide biocide as a function of the ratio of the concentration of hypobromous acid to hypochlorous acid;
  • FIG. 2 is schematic diagram of a biocide water treatment process which employs the present invention
  • FIGS. 3-11 are graphs showing copper corrosion and residual chlorine levels in the cooling system of a commercial power plant.
  • the present invention stems from an unexpected and surprising discovery that the injection of bromide into a chlorination system for treating cooling water to an electric power plant has the effect of substantially decreasing copper corrosion. This was discovered and confirmed by the inventors while they were employed for Nalco Chemical Company and were using the Nalco mobile laboratory to monitor the cooling system of the Miami Fort station of the Cincinnati Gas and Electric Company from July 11, 1986 (FIG. 3) to Aug. 5, 1986.
  • the test results which are illustrated by the graphs in FIGS. 3-11, show the copper corrosion in mills per year in the upper curves and show the residual chlorine in parts per million in the lower curves.
  • the corrosion was measured with an instrument called a corrator, manufactured by Magna Corp., which is a kind of corrosometer which determined corrosion by measuring an electric current between electrodes made of the same copper/nickel alloy as the cooling system under test.
  • the chlorine-bromide-biodispersant mixture was fed from 10:30 until 12:30. During this time period, the total residual chlorine reached a maximum of 0.43 parts per million. The corrosion rate reached a maximum of 0.93 mills per year during this time period.
  • the chlorine-bromide-biodispersant mixture was intentionally turned off at about 10:24, the chlorine continued flowing into the cooling system, and the corrosion rate jumped dramatically from 0.93 mills per year to 1.67 mills per year.
  • the total residual chlorine also increased when only chlorine was injected even though the chlorine feed rate was not increased when the injection of the bromide-biodispersant mixture was shut off. Similar effects are shown in the other test data included in the appendix to the present specification.
  • FIG. 1 there is shown a graph of how various factors are affected by the ratio of the concentration of hypobromous acid to hypochlorous acid during biocide treatment with a chlorine-bromide solution. If chlorine only is injected into the flow of process water, then only hypochlorous acid results so that the concentration ratio is 0%. If an equal molar amount of chlorine and bromide are injected into the process water, then virtually all of the bromide is converted to hypobromous acid and the chlorine becomes converted to chloride. The amount of residual chlorine can be decreased further by injecting an excess of bromide over chlorine, so that, in accordance with Le Chatelier's principle, the conversion reaction between hypochlorous acid and bromide is driven even further toward hypobromous acid production.
  • the biocide activity increases as the concentration ratio reaches 100% hypobromous acid.
  • the cost of producing hypobromous acid increases at an even faster rate, so that absent any factors other than cost and biocide activity, chlorine alone would always be used for biocide water treatment.
  • EPA regulations on the total residual chlorine however, set a TCR limit and to meet this limit bromide must be added to reduce the residual chlorine.
  • the TCR limit results in an optimum concentration ratio of x.
  • the biocide treatment process is modified so that the feed rate of bromide is increased to achieve a certain copper corrosion limit.
  • This copper corrosion limit is dictated by the permissible copper discharge limit divided by the duration of the biocide treatment interval.
  • the inventors made the unexpected and surprising discovery that the copper corrosion decreases as bromide is injected, even though the rate of chlorine injection remains constant.
  • an even higher concentration ratio of hypobromous acid is needed. This higher concentration ratio y is obtained by increasing the chemical feed rate of the bromide solution relative to the chlorine feed rate.
  • FIG. 2 there is shown a schematic diagram of how the present invention can be used for optimizing the water treatment process of a power plant generally designated 10 which obtains cooling water from a source 11 and rejects the heated water to a sink 12.
  • the source 11 and sink 12 for example, are respective inlets and outlets to a river 13.
  • the power plant includes a boiler and turbine 14 which rejects heat to a condenser 15 which receives the flow of water from the source 11 to the sink 12.
  • a computer 16 In order to provide biocide treatment to the cooling water, a computer 16 periodically activates a valve or pump 17 to provide a regulated flow of chlorine from a chlorine source 18 into the flow of cooling water from the source 11 to the condenser 15.
  • the chlorine source for example, includes a supply of gaseous chlorine or sodium hypochloride.
  • the computer 16 In order to provide increased biocide activity and a reduced residual chlorine limit, the computer 16 also activates a control valve or variable rate pump 19 in order to add a bromide and biodispersant solution from a source 20 to the flow of chlorine before the chlorine is injected into the flow of cooling water.
  • the chemical feed rate of bromide from the bromide source 20 is increased or adjusted to obtain a certain copper corrosion limit.
  • the power plant 10 is one of a number of pollution sources along the river 13. Due to this fact, the EPA sets a certain limit on the discharge of copper that is permitted from the power plant.
  • the computer 16 is provided with at least one sensor in order to sense the rate of discharge of copper into the cooling water into the river 13. This sensor, for example, is a corrosometer which indicates the rate of corrosion in the condenser 15. From this rate the amount of copper discharge can be obtained by multiplying the corrosion rate by the internal surface area of the condenser 15, and by the time duration of the chlorine-bromide treatment.
  • a corrosometer reading could be calibrated against the actual discharge of copper from the power plant 10 by obtaining sufficiently large samples of water flowing from the source 11 and also into the sink 12 and measuring the copper concentration in those samples by applying standard chemical techniques of quantitative analysis.
  • the computer 16 determines the average discharge for an entire day's cycle and compares that discharge to the daily limit set by the EPA. Based on this comparison, the set point for the chemical feed rate of bromide is increased or decreased so that during the next day's water treatment cycle the discharge of copper will more closely approximate and will fall within the limit set by the EPA.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US07/081,857 1987-08-05 1987-08-05 Biocide water treatment having reduced copper corrosion Expired - Lifetime US4818413A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US07/081,857 US4818413A (en) 1987-08-05 1987-08-05 Biocide water treatment having reduced copper corrosion
AU20042/88A AU598176B2 (en) 1987-08-05 1988-07-26 Biocide water treatment having reduced copper corrosion
NZ225663A NZ225663A (en) 1987-08-05 1988-08-02 Controlling microorganisms in industrial process waters using bromide salt and a chlorine source
BR8803873A BR8803873A (pt) 1987-08-05 1988-08-04 Processo para tratar aguas de processamento industrial e processo de ajustar a taxa de alimentacao industrial
EP88112729A EP0302501A1 (fr) 1987-08-05 1988-08-04 Traitement biocide de l'eau à corrosion diminuée du cuivre
JP63193561A JPH01119391A (ja) 1987-08-05 1988-08-04 銅腐蝕を減少した殺生物剤水処理方法
EP88121040A EP0373249A1 (fr) 1987-08-05 1988-12-15 Traitement biocide de l'eau, à corrosion réduite du cuivre

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/081,857 US4818413A (en) 1987-08-05 1987-08-05 Biocide water treatment having reduced copper corrosion
EP88121040A EP0373249A1 (fr) 1987-08-05 1988-12-15 Traitement biocide de l'eau, à corrosion réduite du cuivre

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US (1) US4818413A (fr)
EP (2) EP0302501A1 (fr)
JP (1) JPH01119391A (fr)
AU (1) AU598176B2 (fr)
BR (1) BR8803873A (fr)
NZ (1) NZ225663A (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5008075A (en) * 1990-01-16 1991-04-16 Rufolo Paul G Preventative maintenance system for underwater pipes
US5130033A (en) * 1988-06-15 1992-07-14 Total Pool Chemicals Ltd. Relating to the sanitation of swimming pool water
US5141754A (en) * 1990-10-01 1992-08-25 Nalco Chemical Company Zebra mussel control chemical
US5516501A (en) * 1992-05-05 1996-05-14 International Dioxcide Process for the preparation of aqueous solutions of bromine based disinfectants
US5695552A (en) * 1993-12-09 1997-12-09 Research Foundation Of State University Of New York Aquatic antifouling compositions and methods
US5989323A (en) * 1993-12-09 1999-11-23 The Research Foundation Of State University Of New York Aquatic antifouling compositions and methods
US6402957B1 (en) * 1999-10-15 2002-06-11 Seh America, Inc. Bromine biocide removal
US20080279964A1 (en) * 2005-10-27 2008-11-13 Wetegrove Robert L Biofouling control
US20120125079A1 (en) * 2010-11-22 2012-05-24 Martin Seifert Apparatus for on-line continuous chlorine analysis in turbid water and process streams
WO2019135989A1 (fr) 2018-01-03 2019-07-11 Ecolab Usa Inc. Procédé et méthode de réduction de la corrosion métallique dans l'eau

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4818413A (en) * 1987-08-05 1989-04-04 Nalco Chemical Company Biocide water treatment having reduced copper corrosion
GB2326113B (en) * 1995-07-19 1999-06-16 Baker Hughes Ltd Biofouling reduction
DE19627605C1 (de) * 1996-07-09 1997-07-10 Dechema Verfahren zur Erhöhung der Korrosionsbeständigkeit von Werkstoffen auf der Basis TiAl über die Implantation von Halogenionen in die Werkstoffoberfläche
JP5612822B2 (ja) * 2008-12-25 2014-10-22 アクアス株式会社 スライム抑制方法

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US2580809A (en) * 1949-06-14 1952-01-01 Wallace & Tiernan Inc Procedure for purifying aqueous liquid
US3592212A (en) * 1969-12-18 1971-07-13 James A Schleimer Water treatment system
DE2225030A1 (de) * 1971-05-28 1972-12-07 Mitsubishi Heavy Ind Ltd Verfahren zum Schützen von Kupferoder Kupferlegierungsmaterialien, insbesondere von Kühlleitungen, sowie eine Vorrichtung dazu
US4451376A (en) * 1983-07-28 1984-05-29 Nalco Chemical Company Multi-functional hypobromide precursors
US4631530A (en) * 1984-04-02 1986-12-23 Olin Corporation Chemical process monitor
US4659459A (en) * 1985-07-18 1987-04-21 Betz Laboratories, Inc. Automated systems for introducing chemicals into water or other liquid treatment systems
US4643835A (en) * 1985-08-28 1987-02-17 Nalco Chemical Company Asiatic clam control chemical

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5130033A (en) * 1988-06-15 1992-07-14 Total Pool Chemicals Ltd. Relating to the sanitation of swimming pool water
US5008075A (en) * 1990-01-16 1991-04-16 Rufolo Paul G Preventative maintenance system for underwater pipes
US5141754A (en) * 1990-10-01 1992-08-25 Nalco Chemical Company Zebra mussel control chemical
US5516501A (en) * 1992-05-05 1996-05-14 International Dioxcide Process for the preparation of aqueous solutions of bromine based disinfectants
US5695552A (en) * 1993-12-09 1997-12-09 Research Foundation Of State University Of New York Aquatic antifouling compositions and methods
US5989323A (en) * 1993-12-09 1999-11-23 The Research Foundation Of State University Of New York Aquatic antifouling compositions and methods
US6402957B1 (en) * 1999-10-15 2002-06-11 Seh America, Inc. Bromine biocide removal
US6649065B2 (en) 1999-10-15 2003-11-18 Seh America, Inc. Bromine biocide removal
US20080279964A1 (en) * 2005-10-27 2008-11-13 Wetegrove Robert L Biofouling control
US8741157B2 (en) * 2005-10-27 2014-06-03 Nalco Company Biofouling control
US20120125079A1 (en) * 2010-11-22 2012-05-24 Martin Seifert Apparatus for on-line continuous chlorine analysis in turbid water and process streams
US9016110B2 (en) * 2010-11-22 2015-04-28 Nalco Company Apparatus for on-line continuous chlorine analysis in turbid water and process streams
AU2011331983B2 (en) * 2010-11-22 2016-08-11 Nalco Company Apparatus for on-line continuous chlorine analysis in turbid water and process streams
WO2019135989A1 (fr) 2018-01-03 2019-07-11 Ecolab Usa Inc. Procédé et méthode de réduction de la corrosion métallique dans l'eau
US11572628B2 (en) 2018-01-03 2023-02-07 Ecolab Usa Inc. Process and method for reducing metal corrosion in water

Also Published As

Publication number Publication date
NZ225663A (en) 1989-12-21
JPH01119391A (ja) 1989-05-11
EP0373249A1 (fr) 1990-06-20
JPH0244594B2 (fr) 1990-10-04
EP0302501A1 (fr) 1989-02-08
AU598176B2 (en) 1990-06-14
BR8803873A (pt) 1989-02-21
AU2004288A (en) 1989-02-09

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